本實驗室開發的Cu75Sn2多元合金於400～450°C時效時產生顯著的時效硬化，可達HV 328，歸因於富銅基地相中析出富NiAl之BCC固溶相，但導電率並不高，仍難與Cu-Be合金的導電性競爭。根據文獻，在眾多銅合金系統中Cu-Ni-Si合金可同時具備良好的硬度及導電率，相當具有發展的潛力。因此本論文為增強合金析出硬化並同時提升導電率，故結合NiAl、Ni2Si及Ni3Si多種析出物強化的概念開發Cu-Al-Ni-Si合金，並在合金中添加低固溶度的合金元素，如Ti、V及Zr等，以獲得兼具高硬度及導電率的無鈹銅合金。實驗除觀察合金組成及冷滾軋對微結構、時效曲線及導電率影響外，並對滾軋態合金拉伸、耐溫、熱傳導、熱膨脹及室溫磨耗等性質進行研究，以評估新開發合金之應用性及取代傳統銅鈹合金的可行性。
在Cu92合金系列中，針對Al、Ni及Si變量對合金硬度及導電率表現進行研究，其中C92Ni5Zr0.5合金時效硬化效果顯著，其尖峰時效硬度為HV 243，導電率為28.9 %IACS。經冷加工後時效處理，此合金硬度可達到HV 264，但導電率仍可維持在27.1 %IACS。Cu84合金系列中，C84Ni10Zr1合金經冷加工及時效具有最佳之綜合表現，硬度為HV 313，導電率為20.9 %IACS。經TEM分析，此合金於富銅基地相中析出Ni、Si為主的奈米析出物，產生顯著的析出。Cu88合金系列中，將低固溶度的合金元素微量多元添加至合金中，可使硬度接近Cu84合金系列，同時導電率也可達到Cu92合金系列水準，其尖峰時效硬度為HV 290，導電率為26.5 %IACS。
應用性質方面，新開發的合金系列相較於商用銅鈹合金具有較好的耐溫性，經450°C 50小時仍未現時效軟化，而銅鈹合金經400°C 1小時即會出現明顯的過時效軟化。而Cu84Sn1及Cu84V1合金經冷加工後於400°C時效100小時仍維持優於銅鈹合金之硬度，具有良好的抗高溫軟化能力。此外新開發合金也多具備優異的抗磨耗性質及較低的摩擦係數，同時各合金熱膨脹係數皆小於傳統銅鈹合金。整體而言，本研究所開發的九組銅合金於應用方面皆各具競爭優勢，其中有幾組合金的硬度及導電率可取代硬度低於HV 300的Cu-Be合金。

致 謝 i
摘 要 I
目 錄 III
圖目錄 VIII
表目錄 XXI
第一章、前言 1
第二章、文獻回顧 3
2.1純銅基本性質 3
2.2銅合金之用途 4
2.3銅合金之種類[1, 3, 4, 9] 4
2.3.1黃銅 5
2.3.2青銅 8
2.4高硬度高導電率之銅合金發展 12
2.4.1銅鈹合金 12
2.4.2高導電率銅銀、銅鈮合金[16-19] 19
2.4.3銅鎳矽合金[20-28] 23
2.4.4銅鋯合金[29-32] 31
2.4.5銅鈦合金[33-40] 36
2.4.6本研究之背景與目的[6-8] 42
第三章、實驗方法 45
3.1實驗步驟 45
3.2合金設計 46
3.2.1等莫耳Al,Ni,Si,Zr添加之合金系列-Cu92Al2Ni2Si2Zr2、Cu84Al4Ni4Si4Zr4 47
3.2.2減Zr之Cu92合金系列-Cu92Al3.5Ni2Si2Zr0.5、Cu92Al2Ni3.5Si2Zr0.5、Cu92Al2Ni2Si3.5Zr0.5 47
3.2.3 Cu84合金系列-Cu84Al3Ni9Si3Zr1、Cu84Al3Ni9Si3Sn1、Cu84Al3Ni9Si3Ti1、Cu84Al3Ni9Si3V1 48
3.2.4合金改良-Cu92Al0.75Ni5Si1.75Zr0.5、Cu84Al1.5Ni10Si3.5Zr1 48
3.2.5多元微量添加合金-Cu88Al1Ni7.5Si2.5Cr0.5Ti0.1V0.3Zr0.1、Cu89Al1Ni7.5Si2.5 49
3.3真空電弧熔煉 51
3.4均質化處理 51
3.5時效處理 51
3.6滾軋 52
3.7微結構觀察 52
3.7.1 X-ray結晶繞射分析 (XRD) 52
3.7.2光學顯微鏡 (OM) 52
3.7.3掃描式電子顯微鏡 (SEM) 53
3.7.4穿透式電子顯微鏡 (TEM) 53
3.8機械性質量測 54
3.8.1硬度量測 54
3.8.2拉伸試驗 54
3.8.3室溫黏著磨耗試驗 55
3.9室溫電阻量測 58
3.10熱傳導係數量測 60
3.11熱膨脹係數量測 63
第四章、結果與討論 65
4.1 等莫耳Al, Ni, Si, Zr添加之合金微結構及時效曲線 65
4.1.1 Cu92Al2Ni2Si2Zr2 (Cu92合金) 65
4.1.2 Cu84Al4Ni4Si4Zr4 (Cu84合金) 70
4.1.3 探討Cu92及Cu84時效曲線與微結構關聯 74
4.2 減Zr合金微結構及時效曲線-Cu92系列 75
4.2.1 Cu92Al3.5Ni2Si2Zr0.5 (Cu92Al3.5合金) 75
4.2.2 Cu92Al2Ni3.5Si2Zr0.5 (Cu92Ni3.5合金) 80
4.2.3 Cu92Al2Ni2Si3.5Zr0.5 (Cu92Si3.5合金) 85
4.2.4 減鋯Cu92系列合金時效硬化之原因 90
4.3 Cu84系列合金 93
4.3.1 Cu84Al3Ni9Si3Zr1 (Cu84Zr1合金) 93
4.3.2 Cu84Al3Ni9Si3Sn1 (Cu84Sn1合金) 99
4.3.3 Cu84Al3Ni9Si3Ti1 (Cu84Ti1合金) 104
4.3.4 Cu84Al3Ni9Si3V1 (Cu84V1合金) 109
4.3.5 Cu84系列合金時效硬化與微結構比較 114
4.4 合金改良 120
4.4.1 Cu92Al0.75Ni5Si1.75Zr0.5 (Cu92Ni5Zr0.5合金) 120
4.4.2 Cu84Al1.5Ni10Si3.5Zr1 (Cu84Ni10Zr1合金) 126
4.4.2.1 Cu84Al1.5Ni10Si3.5Zr1 TEM分析 132
4.4.3 合金改良的成效與原因 142
4.5 多元微量添加 144
4.5.1 Cu88Al1Ni7.5Si2.5Cr0.5Ti0.1V0.3Zr0.1 (Cu88CrTiVZr合金) 144
4.5.2 Cu89Al1Ni7.5Si2.5 (Cu89合金) 151
4.5.3 微量多元添加的成效 156
4.6 銅合金室溫導電率 158
4.7 冷滾軋對合金性質影響 163
4.7.1 冷滾軋對合金微結構及硬度影響 163
4.7.2 冷滾軋對合金導電率影響 170
4.7.3 熱機處理與再結晶 172
4.8 拉伸測試 177
4.8.1 冷滾軋合金之室溫拉伸 177
4.8.2 熱處理條件對拉伸性質影響 186
4.9 銅合金物理性質與C17200應用性質比較 190
4.9.1 耐溫性 190
4.9.2 熱傳導與密度 192
4.9.3 熱膨脹係數 197
4.9.4 室溫抗磨耗性質 198
4.9.4.1 磨耗面及磨屑分析 198
4.9.4.2 摩擦係數及黏著磨耗阻抗 220
4.10 合金應用潛力 230
第五章、結論 232
第六章、本研究貢獻 236
第七章、建議未來研究方向 237
第八章、參考文獻 238

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